U.S. patent application number 13/040349 was filed with the patent office on 2011-09-15 for hydrophobic thermoplastic polyurethane as a compatilizer for polymer blends for golf balls.
This patent application is currently assigned to NIKE, INC.. Invention is credited to Bradley C. Tutmark.
Application Number | 20110224019 13/040349 |
Document ID | / |
Family ID | 44080375 |
Filed Date | 2011-09-15 |
United States Patent
Application |
20110224019 |
Kind Code |
A1 |
Tutmark; Bradley C. |
September 15, 2011 |
Hydrophobic Thermoplastic Polyurethane As A Compatilizer For
Polymer Blends For Golf Balls
Abstract
A golf ball has a layer comprising a compatibilized blend of
thermoplastic polyurethane, polyolefin, and hydrophobic
thermoplastic polyurethane. The layer may be part of the cover, for
example an inner layer of a two-layer cover layer. The layer may be
an intermediate layer between the core and the cover.
Inventors: |
Tutmark; Bradley C.; (Aloha,
OR) |
Assignee: |
NIKE, INC.
Beaverton
OR
|
Family ID: |
44080375 |
Appl. No.: |
13/040349 |
Filed: |
March 4, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
61312282 |
Mar 10, 2010 |
|
|
|
Current U.S.
Class: |
473/371 ;
264/279.1; 473/378 |
Current CPC
Class: |
A63B 37/0031 20130101;
A63B 37/0093 20130101; A63B 37/0003 20130101; A63B 37/0038
20130101; A63B 37/0023 20130101; A63B 37/0043 20130101 |
Class at
Publication: |
473/371 ;
473/378; 264/279.1 |
International
Class: |
A63B 37/00 20060101
A63B037/00; A63B 37/12 20060101 A63B037/12 |
Claims
1. A golf ball, comprising: a core; an intermediate layer, and a
cover layer; wherein the intermediate layer comprises a
compatibilized blend comprising thermoplastic elastomer and a
polyolefin, and an effective amount of a compatibilizing agent
comprising hydrophobic thermoplastic polyurethane.
2. The golf ball of claim 1 wherein the hydrophobic thermoplastic
polyurethane comprises the reaction product of (1) a hydrophobic
polyol, (2) a polyisocyanate, and (3) a linear chain extender
containing 5 carbon atoms or 7 to 12 carbon atoms; wherein the
hydrophobic polyol has a number average molecular weight which is
within the range of about 1,000 to about 4,000; wherein the semi
crystalline, thermoplastic polyurethane has a weight average
molecular weight which is within the range of 50,000 to 1,000,000;
and wherein the semi crystalline, thermoplastic polyurethane has a
melting point which is within the range of 80.degree. C. to
150.degree. C.
3. The golf ball of claim 1 wherein the thermoplastic elastomer is
thermoplastic polyurethane.
4. The golf ball of claim 1 wherein the intermediate layer has a
Water Vapor Transmission Rate (WVTR) of less than 1300 g/m.sup.2
after 168 hrs at 25 C and 50% relative humidity.
5. The golf ball of claim 1 wherein the intermediate layer has a
Water Vapor Transmission Rate (WVTR) of less than 1000 g/m.sup.2
after 168 hrs at 25 C and 50% relative humidity.
6. The golf ball of claim 1 wherein the intermediate layer has a
Shore D hardness between 20 and 65.
7. The golf ball of claim 1 wherein the intermediate layer has a
specific gravity of greater than 0.80.
8. The golf ball of claim 1 wherein the compatibilized blend is
prepared with thermoplastic elastomer having a Shore D hardness of
between about 20 and about 65.
9. The golf ball of claim 1 wherein the compatibilized blend is
prepared with thermoplastic elastomer having a weight average
molecular weight of from about 20,000 to about 500,000.
10. The golf ball of claim 1 wherein the compatibilized blend
comprises from about 5 percent to about 95 percent by weight
thermoplastic elastomer and from about 95 percent by weight to
about 5 percent by weight polyolefin based on total weight of the
thermoplastic elastomer and the polyolefin in the blend.
11. The golf ball of claim 1 wherein the effective amount of the
compatibilized agent is from about 0.25 to about 15 parts by weight
per 100 parts by total weight of the thermoplastic elastomer and
the polyolefin in the blend.
12. A golf ball, comprising: a core; and a cover; wherein the cover
comprises at least one layer comprising a compatibilized blend
comprising thermoplastic elastomer and a polyolefin, and an
effective amount of a compatibilizing agent comprising hydrophobic
thermoplastic polyurethane.
13. The golf ball of claim 12 wherein the hydrophobic thermoplastic
polyurethane comprises the reaction product of (1) a hydrophobic
polyol, (2) a polyisocyanate, and (3) a linear chain extender
containing 5 carbon atoms or 7 to 12 carbon atoms; wherein the
hydrophobic polyol has a number average molecular weight which is
within the range of about 1,000 to about 4,000; wherein the semi
crystalline, thermoplastic polyurethane has a weight average
molecular weight which is within the range of 50,000 to 1,000,000;
and wherein the semi crystalline, thermoplastic polyurethane has a
melting point which is within the range of 80.degree. C. to
150.degree. C.
14. The golf ball of claim 12 wherein the thermoplastic elastomer
is thermoplastic polyurethane.
15. The golf ball of claim 12 wherein the cover layer has a Water
Vapor Transmission Rate (WVTR) of less than 1300 g/m.sup.2 after
168 hrs.
16. The golf ball of claim 12 wherein the intermediate layer has a
Water Vapor Transmission Rate (WVTR) of less than 1000 g/m.sup.2
after 168 hrs at 25 C and 50% relative humidity.
17. The golf ball of claim 12 wherein the cover layer has a Shore D
hardness between 20 and 50.
18. The golf ball of claim 12 wherein the cover layer has a
specific gravity of greater than 0.80.
19. The golf ball of claim 12 wherein the compatibilized blend is
prepared with thermoplastic elastomer having a Shore D hardness of
between about 20 and about 65.
20. The golf ball of claim 12 wherein the compatibilized blend is
prepared with thermoplastic elastomer having a weight average
molecular weight of from about 20,000 to about 500,000.
21. The golf ball of claim 12 wherein the compatibilized blend
comprises from about 5 percent to about 95 percent by weight
thermoplastic elastomer and from about 95 percent by weight to
about 5 percent by weight polyolefin based on total weight of the
thermoplastic elastomer and the polyolefin in the blend.
22. The golf ball of claim 12 wherein the effective amount of the
compatibilized agent is from about 0.25 to about 15 parts by weight
per 100 parts by total weight of the thermoplastic elastomer and
the polyolefin in the blend.
23. A method of preparing a golf ball comprising applying a
compatibilized blend to a golf ball as an intermediate layer or
cover layer, the moisture barrier layer comprising thermoplastic
elastomer and a polyolefin, and an effective amount of a
compatibilizing agent comprising hydrophobic thermoplastic
polyurethane.
24. The method of claim 23 wherein the layer comprising the
compatibilized blend is molded onto a core or intermediate layer of
the golf ball.
Description
[0001] This application claims benefit from U.S. Provisional
application No. 61/312,282, filed Mar. 10, 2010, the whole contents
of which are incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to golf balls. Particular
aspects of this invention relate to golf balls prepared with
polymer blends prepared with hydrophobic thermoplastic polyurethane
compatibilizing agents.
BACKGROUND
[0003] Golf is enjoyed by a wide variety of players--players of
different genders and dramatically different ages and/or skill
levels. Golf is unique in the sporting world in that such diverse
collections of players can play together in golf events, even in
direct competition with one another (e.g., using handicapped
scoring, different tee boxes, in team formats, etc.), and still
enjoy the golf outing or competition. These factors, together with
the increased availability of golf programming on television (e.g.,
golf tournaments, golf news, golf history, and/or other golf
programming) and the rise of well known golf superstars, at least
in part, have increased golf's popularity in recent years, both in
the United States and across the world.
[0004] Golfers at all skill levels seek to improve their
performance, lower their golf scores, and reach that next
performance "level." Manufacturers of all types of golf equipment
have responded to these demands, and in recent years, the industry
has witnessed dramatic changes and improvements in golf equipment.
For example, a wide range of different golf ball models now are
available, with balls designed to complement specific swing speeds
and/or other player characteristics or preferences, e.g., with some
balls designed to fly farther and/or straighter; some designed to
provide higher or flatter trajectories; some designed to provide
more spin, control, and/or feel (particularly around the greens);
some designed for faster or slower swing speeds; etc. A host of
swing and/or teaching aids also are available on the market that
promise to help lower one's golf scores.
[0005] Being the sole instrument that sets a golf ball in motion
during play, golf clubs also have been the subject of much
technological research and advancement in recent years. For
example, the market has seen dramatic changes and improvements in
putter designs, golf club head designs, shafts, and grips in recent
years. Additionally, other technological advancements have been
made in an effort to better match the various elements and/or
characteristics of the golf club and characteristics of a golf ball
to a particular user's swing features or characteristics (e.g.,
club fitting technology, ball launch angle measurement technology,
ball spin rate measurement technology, ball fitting technology,
etc.).
[0006] Modern golf balls generally comprise either a one-piece
construction or several layers including an outer cover surrounding
a core. Some golf ball layers include a thermoplastic elastomer
(e.g. polyurethane (TPU)) or polyolefin type materials. The
urethane-type polymer is preferred by skilled players and
professionals due to its high spin characteristics with short irons
and around the green. However, urethane cover materials affect the
ball in a negative way in that the Water Vapor Transmission Rate
(WVTR) is approximately 1 to 2 orders of magnitude greater than
(ionomer) materials. This problem arises when moisture penetrates
the ball over time, hardening the ball's rubber core or any other
rubber layer. This will ultimately change the balls performance.
Polyolefins are desired for their excellent rebound
characteristics. However, polyolefin-based materials tend to have
poor scuff performance, i.e. they are scuffed easily when struck by
the face of a golf club. Particularly wedges and short irons which
are designed to generate spin on the ball.
[0007] It would be desirable to combine a thermoplastic elastomer
such as TPU and polyolefins to provide a polymer blend having both
excellent spin and durability characteristics as well as excellent
rebound characteristics. However TPU and polyolefin are generally
immiscible and hence incompatible. This results in unacceptable
materials having poor properties. Moreover, a layer prepared from
this type of blend tends to delaminate within itself. It would be
desirable to provide a blend of TPU and polyolefins in order to
provide the desired characteristics from each.
[0008] While the industry has witnessed dramatic changes and
improvements to golf equipment in recent years, some players
continue to look for increased distance on their golf shots,
particularly on their drives or long iron shots, and/or improved
spin or control of their shots, particularly around the greens.
Accordingly, there is room in the art for further advances in golf
technology.
SUMMARY
[0009] The following presents a general summary of aspects of the
disclosure in order to provide a basic understanding of the
disclosure and various aspects of it. This summary is not intended
to limit the scope of the disclosure in any way, but it simply
provides a general overview and context for the more detailed
description that follows.
[0010] Aspects of this invention are directed to golf balls having
at least one layer prepared with a compatibilized blend comprising
thermoplastic elastomer and a polyolefin, and an effective amount
of a compatibilizing agent comprising hydrophobic thermoplastic
polyurethane.
[0011] Aspects of this invention are directed to golf balls having
at least one layer prepared with a compatibilized blend comprising
thermoplastic polyurethane (TPU) and a polyolefin, and an effective
amount of a compatibilizing agent comprising hydrophobic
thermoplastic polyurethane.
[0012] Other aspects of this invention are directed to methods for
applying a layer comprising the compatibilized blend.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] A more complete understanding of the present invention and
certain advantages thereof may be acquired by referring to the
following detailed description in consideration with the
accompanying drawings, in which:
[0014] FIG. 1 schematically illustrates a golf ball having
dimples.
[0015] FIG. 2 schematically illustrates a cross-sectional view of a
golf ball in accordance with FIG. 1.
[0016] FIG. 3 schematically illustrates another cross-sectional
view of a golf ball in accordance with FIG. 1.
[0017] FIG. 4 provides Moisture Vapor Transmission Rates for
various Hydrophobic TPU blends.
[0018] The reader is advised that the various parts shown in these
drawings are not necessarily drawn to scale.
DETAILED DESCRIPTION
[0019] In the following description of various example structures,
reference is made to the accompanying drawings, which form a part
hereof, and in which are shown by way of illustration various
example golf ball structures. Additionally, it is to be understood
that other specific arrangements of parts and structures may be
utilized and structural and functional modifications may be made
without departing from the scope of the present invention. Also,
while terms such as "top," "bottom," "front," "back," "rear,"
"side," "underside," "overhead," and the like may be used in this
specification to describe various example features and elements of
the invention, these terms are used herein as a matter of
convenience, e.g., based on the example orientations shown in the
figures and/or the orientations in typical use. Nothing in this
specification should be construed as requiring a specific three
dimensional or spatial orientation of structures.
A. General Description of Golf Balls and Manufacturing Systems and
Methods
[0020] Golf balls may be of varied construction, e.g., one-piece
balls, two-piece balls, three-piece balls (including wound balls),
four-piece balls, five-piece balls, etc. The difference in play
characteristics resulting from these different types of
constructions can be quite significant. Generally, golf balls may
be classified as solid or wound balls. Solid balls that have a
two-piece construction, typically a cross-linked rubber core, e.g.,
polybutadiene cross-linked with zinc diacrylate and/or similar
cross-linking agents, encased by a blended cover, e.g., ionomer
resins, are popular with many average recreational golfers. The
combination of the core and cover materials provide a relatively
"hard" ball that is virtually indestructible by golfers and one
that imparts a high initial velocity to the ball, resulting in
improved distance. Because the materials from which the ball is
formed are very rigid, two-piece balls tend to have a hard "feel"
when struck with a club. Likewise, due to their hardness, these
balls have a relatively low spin rate, which also helps provide
greater distance.
[0021] Wound balls are generally constructed from a liquid or solid
center surrounded by tensioned elastomeric material and covered
with a durable cover material, e.g., ionomer resin, or a softer
cover material, e.g., balata or polyurethane. Wound balls are
generally thought of as performance golf balls and have good
resiliency, desirable spin characteristics, and good "feel" when
struck by a golf club. However, wound balls are generally difficult
to manufacture as compared to solid golf balls.
[0022] More recently, three- and four-piece balls have gained
popularity, both as balls for average recreational golfers as well
as performance balls for professional and other elite level
players. Such balls typically include a core (optionally a
multi-part core, such as an inner core and an outer core), one or
more mantle or intermediate layers (also called "inner cover"
layers), and an outer cover layer.
[0023] A variety of golf balls have been designed to provide
particular playing characteristics. These characteristics generally
include the initial velocity and spin of the golf ball, which can
be optimized for various types of players. For instance, certain
players prefer a ball that has a high spin rate in order to control
and stop the golf ball around the greens. Other players prefer a
ball that has a low spin rate and high resiliency to maximize
distance. Generally, a golf ball having a hard core and a soft
cover will have a high spin rate. Conversely, a golf ball having a
hard cover and a soft core will have a low spin rate. Golf balls
having a hard core and a hard cover generally have very high
resiliency for distance, but they may "feel" hard and be difficult
to control around the greens.
[0024] The carry distance of some conventional two-piece balls has
been improved by altering the typical single layer core and single
cover layer construction to provide a multi-layer ball, e.g., a
dual cover layer, dual core layer, and/or a ball having an
intermediate layer disposed between the cover and the core. Three-
and four-piece balls are now commonly found and commercially
available. Aspects of this invention may be applied to all types of
ball constructions, including the wound, solid, and/or multi-layer
ball constructions described above.
[0025] FIG. 1 is a perspective view of a solid golf ball 100
according to an aspect of the invention. Golf ball 100 may be
generally spherical in shape with a plurality of dimples 102
arranged on the outer surface 108 of golf ball 100 in a pattern
112.
[0026] Internally, golf ball 100 may be generally constructed as a
multilayer solid golf ball, having any desired number of pieces. In
other words, multiple layers of material may be fused, blended, or
compressed together to form the ball. The physical characteristics
of a golf ball may be determined by the combined properties of the
core layer(s), any optional mantle layers, and the cover. The
physical characteristics of each of these components may be
determined by their respective chemical compositions. The majority
of components in golf balls comprise oligomers or polymers. The
physical properties of oligomers and polymers may be highly
dependent on their composition, including the monomer units
included, molecular weight, degree of cross-linking, etc. Examples
of such properties may include solubility, viscosity, specific
gravity (SG), elasticity, hardness (e.g., as measured as Shore D
hardness), rebound resilience, scuff resistance, etc. The physical
properties of the oligomers and polymers used may also affect the
industrial processes used to make the components of the golf ball.
For example, where injection molding is the processing method used,
extremely viscous materials may slow down the process and thus
viscosity may become a limiting step of production.
[0027] As shown in FIG. 2, one aspect of such a golf ball (referred
to generally as 200) includes a core 204, a cover 208, and an
intermediate layer 206 between core 204 and cover 208. Cover 208
surrounds, encloses, encompasses, etc., the core and any other
internal layers of the ball. Cover 208 has an outer surface that
may include a dimple pattern comprising a plurality of dimples.
[0028] As shown in FIG. 3, another aspect of such a golf ball
(referred to generally as 300) includes a core 304, a cover 308,
and intermediate layers 306 and 310 between core 304 and cover 308.
Cover 308 surrounds, encloses, encompasses, etc., the core and any
other internal layers of the ball. Cover 308 has an outer surface
that may include a dimple pattern comprising a plurality of
dimples.
The Center
[0029] A golf ball may be formed, for example, with a center having
a low compression, but still exhibit a finished ball COR and
initial velocity approaching that of conventional two-piece
distance balls. The center may have, for example, a compression of
about 60 or less. The finished balls made with such centers have a
COR, measured at an inbound speed of 125 ft./s., of about 0.795 to
about 0.815. "COR" refers to Coefficient of Restitution, which is
obtained by dividing a ball's rebound velocity by its initial
(i.e., incoming) velocity. This test is performed by firing the
samples out of an air cannon at a vertical steel plate over a range
of test velocities (e.g., from 75 to 150 ft/s). A golf ball having
a high COR dissipates a smaller fraction of its total energy when
colliding with the plate and rebounding therefrom than does a ball
with a lower COR.
[0030] The terms "points" and "compression points" refer to the
compression scale or the compression scale based on the ATTI
Engineering Compression Tester. This scale, which is well known to
persons skilled in the art, is used in determining the relative
compression of a center or ball.
[0031] The center may have, for example, a Shore C hardness of
about 40 to about 80. The center may have a diameter of about 0.75
inches to about 1.68 inches. The base composition for forming the
center may include, for example, polybutadiene and about 20 to 50
parts of a metal salt diacrylate, dimethacrylate, or
monomethacrylate. If desired, the polybutadiene can also be mixed
with other elastomers known in the art, such as natural rubber,
styrene butadiene, and/or isoprene, in order to further modify the
properties of the center. When a mixture of elastomers is used, the
amounts of other constituents in the center composition are usually
based on 100 parts by weight of the total elastomer mixture. In
other examples, the center (or core) may be made from resin
materials, such as HPF resins (optionally with barium sulfate
included therein), which are commercially available from E.I.
DuPont de Nemours and Company of Wilmington, Del.
[0032] Metal salt diacrylates, dimethacrylates, and
monomethacrylates include without limitation those wherein the
metal is magnesium, calcium, zinc, aluminum, sodium, lithium or
nickel. Zinc diacrylate, for example, provides golf balls with a
high initial velocity in the United States Golf Association
("USGA") test.
[0033] Free radical initiators often are used to promote
cross-linking of the metal salt diacrylate, dimethacrylate, or
monomethacrylate and the polybutadiene. Suitable free radical
initiators include, but are not limited to peroxide compounds, such
as dicumyl peroxide; 1,1-di(t-butylperoxy) 3,3,5-trimethyl
cyclohexane; bis(t-butylperoxy) diisopropylbenzene;
2,5-dimethyl-2,5'di(t-butylperoxy) hexane; or di-t-butyl peroxide;
and mixtures thereof. The initiator(s) at 100 percent activity may
be added in an amount ranging from about 0.05 to about 2.5 pph
based upon 100 parts of butadiene, or butadiene mixed with one or
more other elastomers. Often the amount of initiator added ranges
from about 0.15 to about 2 pph, and more often from about 0.25 to
about 1.5 pph. The golf ball centers may incorporate 5 to 50 pph of
zinc oxide (ZnO) in a zinc diacrylate-peroxide cure system that
cross-links polybutadiene during the core molding process.
[0034] The center compositions may also include fillers, added to
the elastomeric (or other) composition to adjust the density and/or
specific gravity of the center. Non-limiting examples of fillers
include zinc oxide, barium sulfate, and regrind, e.g., recycled
core molding matrix ground to about 30 mesh particle size. The
amount and type of filler utilized is governed by the amount and
weight of other ingredients in the composition, bearing in mind a
maximum golf ball weight of 1.620 oz has been established by the
USGA. Fillers usually range in specific gravity from about 2.0 to
about 5.6. The amount of filler in the center may be lower such
that the specific gravity of the center is decreased.
[0035] The specific gravity of the center may range, for example,
from about 0.8 to about 1.3, depending upon such factors as the
size of the center, cover, intermediate layer and finished ball, as
well as the specific gravity of the cover and intermediate layer.
Other components such as accelerators, e.g., tetra methylthiuram,
processing aids, processing oils, plasticizers, dyes and pigments,
antioxidants, as well as other additives well known to the skilled
artisan may also be used in amounts sufficient to achieve the
purpose for which they are typically used.
[0036] Intermediate Layer(s)
[0037] The golf ball also may have one or more intermediate layers
formed, for example, from dynamically vulcanized thermoplastic
elastomers, functionalized styrene-butadiene elastomers,
thermoplastic rubbers, polybutadiene rubbers, natural rubbers,
thermoset elastomers, thermoplastic urethanes, metallocene
polymers, thermoset urethanes, ionomer resins, or blends thereof.
For example, an intermediate layer may include a thermoplastic or
thermoset polyurethane. Non-limiting of commercially available
dynamically vulcanized thermoplastic elastomers include
SANTOPRENE.RTM., SARLINK.RTM., VYRAM.RTM., DYTRON.RTM., and
VISTAFLEX.RTM.. SANTOPRENE.RTM. is a dynamically vulcanized
PP/EPDM. Examples of functionalized styrene-butadiene elastomers,
i.e., styrene-butadiene elastomers with functional groups such as
maleic anhydride or sulfonic acid, include KRATON FG-1901x and
FG-1921x, which are available from the Shell Corporation of
Houston, Tex.
[0038] Examples of suitable thermoplastic polyurethanes include
ESTANE.RTM. 58133, ESTANE.RTM. 58134 and ESTANE.RTM. 58144, which
are commercially available from Lubrizol of Cleveland, Ohio.
[0039] Examples of metallocene polymers, i.e., polymers formed with
a metallocene catalyst, include those commercially available from
Sentinel Products of Hyannis, Mass. Suitable thermoplastic
polyesters include polybutylene terephthalate. Thermoplastic
ionomer resins may be obtained by providing a cross metallic bond
to polymers of monoolefin with at least one member selected from
the group consisting of unsaturated mono- or di-carboxylic acids
having 3 to 12 carbon atoms and esters thereof (the polymer
contains 1 to 50 percent by weight of the unsaturated mono- or
di-carboxylic acid and/or ester thereof). More particularly, low
modulus ionomers such as acid-containing ethylene copolymer
ionomers, include E/X/Y copolymers where E is ethylene, X is a
softening comonomer such as acrylate or methacrylate. Non-limiting
examples of ionomer resins include SURLYN.RTM. and IOTEK.RTM.,
which are commercially available from DuPont and Exxon,
respectively.
[0040] Alternatively, the intermediate layer(s) may be a blend of a
first and a second component wherein the first component is a
dynamically vulcanized thermoplastic elastomer, a functionalized
styrene-butadiene elastomer, a thermoplastic or thermoset
polyurethane or a metallocene polymer and the second component is a
material such as a thermoplastic or thermoset polyurethane, a
thermoplastic polyetherester or polyetheramide, a thermoplastic
ionomer resin, a thermoplastic polyester, another dynamically
vulcanized elastomer, another a functionalized styrene-butadiene
elastomer, another a metallocene polymer or blends thereof. At
least one of the first and second components may include a
thermoplastic or thermoset polyurethane.
[0041] One or more intermediate layers also may be formed from a
blend containing an ethylene methacrylic/acrylic acid copolymer.
Non-limiting examples of acid-containing ethylene copolymers
include ethylene/acrylic acid; ethylene/methacrylic acid;
ethylene/acrylic acid/n- or isobutyl acrylate; ethylene/methacrylic
acid/n- or iso-butyl acrylate; ethylene/acrylic acid/methyl
acrylate; ethylene/methacrylic acid/methyl acrylate;
ethylene/acrylic acid/iso-bornyl acrylate or methacrylate and
ethylene/methacrylic acid/isobornyl acrylate or methacrylate.
Examples of commercially available ethylene methacrylic/acrylic
acid copolymers include NUCREL.RTM. polymers, available from
DuPont.
[0042] Alternatively, the intermediate layer(s) may be formed from
a blend which includes an ethylene methacrylic/acrylic acid
copolymer and a second component which includes a thermoplastic
material. Suitable thermoplastic materials for use in the
intermediate blend include, but are not limited to, polyesterester
block copolymers, polyetherester block copolymers, polyetheramide
block copolymers, ionomer resins, dynamically vulcanized
thermoplastic elastomers, styrene-butadiene elastomers with
functional groups such as maleic anhydride or sulfonic acid
attached, thermoplastic polyurethanes, thermoplastic polyesters,
metallocene polymers, and/or blends thereof.
[0043] An intermediate layer often has a specific gravity of about
0.80 or more. In some examples the intermediate layer has a
specific gravity greater than 1.0, e.g., ranging from about 1.02 to
about 1.3. Specific gravity of the intermediate layer may be
adjusted, for example, by adding a filler such as barium sulfate,
zinc oxide, titanium dioxide and combinations thereof.
[0044] The intermediate layer blend may have a flexural modulus of
less than about 15,000 psi, often from about 5,000 to about 8,000
psi. The intermediate layers often have a Shore D hardness of about
35 to 70. The intermediate layer and core construction together may
have a compression of less than about 65, often from about 50 to
about 65. Usually, the intermediate layer has a thickness from
about 0.020 inches to about 0.2 inches. The golf balls may include
a single intermediate layer or a plurality of intermediate layers.
In the case where a ball includes a plurality of intermediate
layers, a first intermediate layer outside the core may include,
for example, a thermoplastic material or a rubber material
(synthetic or natural) having a hardness greater than that of the
core.
[0045] A second intermediate layer may be disposed around the first
intermediate layer and may have a greater hardness than that of the
first intermediate layer. The second intermediate layer may be
formed of materials such as polyether or polyester thermoplastic
urethanes, thermoset urethanes, and ionomers such as
acid-containing ethylene copolymer ionomers.
[0046] In addition, if desired, a third intermediate layer (or even
more layers) may be disposed in between the first and second
intermediate layers. The third intermediate layer may be formed of
the variety of materials as discussed above. For example, the third
intermediate layer may have a hardness greater than that of the
first intermediate layer.
The Cover Layer
[0047] A golf ball also typically has a cover layer that includes
one or more layers of a thermoplastic or thermosetting material. A
variety of materials may be used such as ionomer resins,
thermoplastic polyurethanes, balata and blends thereof.
[0048] The cover may be formed of a composition including very low
modulus ionomers (VLMIs). As used herein, the term "very low
modulus ionomers," or the acronym "VLMIs," are those ionomer resins
further including a softening comonomer X, commonly a
(meth)acrylate ester, present from about 10 weight percent to about
50 weight percent in the polymer. VLMIs are copolymers of an
.alpha.-olefin, such as ethylene, a softening agent, such as
n-butyl-acrylate or iso-butyl-acrylate, and an .alpha.,
.beta.-unsaturated carboxylic acid, such as acrylic or methacrylic
acid, where at least part of the acid groups are neutralized by a
magnesium cation. Other examples of softening comonomers include
n-butyl methacrylate, methyl acrylate, and methyl methacrylate.
Generally, a VLMI has a flexural modulus from about 2,000 psi to
about 10,000 psi. VLMIs are sometimes referred to as "soft"
ionomers.
[0049] Ionomers, such as acid-containing ethylene copolymer
ionomers, include E/X/Y copolymers where E is ethylene, X is a
softening comonomer such as acrylate or methacrylate present in 0
to 50 weight percent of the polymer, and Y is acrylic or
methacrylic acid present in 5 to 35 (often 10 to 20) weight percent
of the polymer, wherein the acid moiety is neutralized 1 to 90
percent (usually at least 40 percent) to form an ionomer by a
cation such as lithium, sodium, potassium, magnesium, calcium,
barium, lead, tin, zinc or aluminum, or a combination of such
cations, lithium, sodium and zinc being the most preferred.
Specific acid-containing ethylene copolymers include
ethylene/acrylic acid, ethylene/methacrylic acid, ethylene/acrylic
acid/n-butyl acrylate, ethylene/methacrylic acid/n-butyl acrylate,
ethylene/methacrylic acid/iso-butyl acrylate, ethylene/acrylic
acid/iso-butyl acrylate, ethylene/methacrylic acid/n-butyl
methacrylate, ethylene/acrylic acid/methyl methacrylate,
ethylene/acrylic acid/methyl acrylate, ethylene/methacrylic
acid/methyl acrylate, ethylene/methacrylic acid/methyl
methacrylate, and ethylene/acrylic acid/n-butyl methacrylate.
[0050] To aid in the processing of the cover stock, ionomer resins
may be blended in order to obtain a cover having desired
characteristics. For this reason, the cover may be formed from a
blend of two or more ionomer resins. The blend may include, for
example, a very soft material and a harder material. Ionomer resins
with different melt flow indexes are often employed to obtain the
desired characteristics of the cover stock. SURLYN.RTM. 8118, 7930
and 7940 have melt flow indices of about 1.4, 1.8, and 2.6 g/10
min., respectively. SURLYN.RTM. 8269 and SURLYN.RTM. 8265 each have
a melt flow index of about 0.9 g/10 min. A blend of ionomer resins
may be used to form a cover having a melt flow index, for example,
of from about 1 to about 3 g/10 min. The cover layer may have a
Shore D hardness, for example, ranging from about 20 to about
80.
[0051] The cover also may include thermoplastic and/or thermoset
materials. For example, the cover may include a thermoplastic
material such as urethane or polyurethane. Polyurethane is a
product of a reaction between a polyurethane prepolymer and a
curing agent. The polyurethane prepolymer is a product formed by a
reaction between a polyol and a diisocyanate. Often, a catalyst is
employed to promote the reaction between the curing agent and the
polyurethane prepolymer. In the case of cast polyurethanes, the
curing agent is typically either a diamine or glycol.
[0052] As another example, a thermoset cast polyurethane may be
used. Thermoset cast polyurethanes are generally prepared using a
diisocyanate, such as 2,4-toluene diisocyanate (TDI),
methylenebis-(4-cyclohexyl isocyanate) (HMDI), or para-phenylene
diisocyanate ("PPDI") and a polyol which is cured with a polyamine,
such as methylenedianiline (MDA), or a trifunctional glycol, such
as trimethylol propane, or tetrafunctional glycol, such as
N,N,N',N'-tetrakis(2-hydroxpropyl)ethylenediamine. Other suitable
thermoset materials include, but are not limited to, thermoset
urethane ionomers and thermoset urethane epoxies. Other examples of
thermoset materials include polybutadiene, natural rubber,
polyisoprene, styrene-butadiene, and styrene-propylene-diene
rubber.
[0053] When the cover includes more than one layer, e.g., an inner
cover layer and an outer cover layer, various constructions and
materials are suitable. For example, an inner cover layer may
surround the intermediate layer with an outer cover layer disposed
thereon or an inner cover layer may surround a plurality of
intermediate layers. When using an inner and outer cover layer
construction, the outer cover layer material may be a thermoset
material that includes at least one of a castable reactive liquid
material and reaction products thereof, as described above, and may
have a hardness from about 30 Shore D to about 60 Shore D.
[0054] The inner cover layer may be formed from a wide variety of
hard (e.g., about 50 Shore D or greater), high flexural modulus
resilient materials, which are compatible with the other materials
used in the adjacent layers of the golf ball. The inner cover layer
material may have a flexural modulus of about 65,000 psi or
greater. Suitable inner cover layer materials include the hard,
high flexural modulus ionomer resins and blends thereof, which may
be obtained by providing a cross metallic bond to polymers of
monoolefin with at least one member selected from the group
consisting of unsaturated mono- or di-carboxylic acids having 3 to
12 carbon atoms and esters thereof (the polymer contains 1 to 50
percent by weight of the unsaturated mono- or di-carboxylic acid
and/or ester thereof). More particularly, such acid-containing
ethylene copolymer ionomer component includes E/X/Y copolymers
where E is ethylene, X is a softening comonomer such as acrylate or
methacrylate present in 0-50 weight percent of the polymer, and Y
is acrylic or methacrylic acid present in 5-35 weight percent of
the polymer, wherein the acid moiety is neutralized about 1-90
percent to form an ionomer by a cation such as lithium, sodium,
potassium, magnesium, calcium, barium, lead, tin, zinc, or
aluminum, or a combination of such cations. Specific examples of
acid-containing ethylene copolymers include ethylene/acrylic acid,
ethylene/methacrylic acid, ethylene/acrylic acid/n-butyl acrylate,
ethylene/methacrylic acid/n-butyl acrylate, ethylene/methacrylic
acid/iso-butyl acrylate, ethylene/acrylic acid/iso-butyl acrylate,
ethylene/methacrylic acid/n-butyl methacrylate, ethylene/acrylic
acid/methyl methacrylate, ethylene/acrylic acid/methyl acrylate,
ethylene/methacrylic acid/methyl acrylate, ethylene/methacrylic
acid/methyl methacrylate, and ethylene/acrylic acid/n-butyl
methacrylate.
[0055] Examples of other suitable inner cover materials include
thermoplastic or thermoset polyurethanes, polyetheresters,
polyetheramides, or polyesters, dynamically vulcanized elastomers,
functionalized styrene-butadiene elastomers, metallocene polymers,
polyamides such as nylons, acrylonitrile butadiene-styrene
copolymers (ABS), or blends thereof.
Manufacturing Process
[0056] While golf balls in accordance with examples of this
invention may be made in any desired manner without departing from
this invention, including in conventional manners as are known and
used in the art, one common technique for manufacturing golf balls
is a laminate process. In order to form multiple layers around the
center, a laminate is first formed. The laminate includes at least
two layers and sometimes includes three layers. The laminate may be
formed by mixing uncured core material to be used for each layer
and calendar rolling the material into thin sheets. Alternatively,
the laminate may be formed by mixing uncured intermediate layer
material and rolling the material into sheets. The laminate sheets
may be stacked together to form a laminate having three layers,
using calender rolling mills. Alternatively, the sheets may be
formed by extrusion.
[0057] A laminate also may be formed using an adhesive between each
layer of material. For example, an epoxy resin may be used as
adhesive. The adhesive should have good shear and tensile strength,
for example, a tensile strength over about 1500 psi. The adhesive
often has a Shore D hardness of less than about 60 when cured. The
adhesive layer applied to the sheets should be very thin, e.g.,
less than about 0.004 inches thick.
[0058] Preferably, each laminate sheet is formed to a thickness
that is slightly larger than the thickness of the layers in the
finished golf ball. Each of these thicknesses can be varied, but
all have a thickness of preferably less than about 0.1 inches. The
sheets should have very uniform thicknesses.
[0059] The next step in the method is to form multiple layers
around the center. This may be accomplished by placing two
laminates between a top mold and a bottom mold. The laminates may
be formed to the cavities in the mold halves. The laminates then
may be cut into patterns that, when joined, form a laminated layer
around the center. For example, the laminates may be cut into
figure 8-shaped or barbell-like patterns, similar to a baseball or
a tennis ball cover. Other patterns may be used, such as curved
triangles, hemispherical cups, ovals, or other patterns that may be
joined together to form a laminated layer around the center. The
patterns may then be placed between molds and formed to the
cavities in the mold halves. A vacuum source often is used to form
the laminates to the mold cavities so that uniformity in layer
thickness is maintained.
[0060] After the laminates have been formed to the cavities, the
centers are then inserted between the laminates. The laminates are
then compression molded about the center under conditions of
temperature and pressure that are well known in the art. The mold
halves usually have vents to allow flowing of excess layer material
from the laminates during the compression molding process. As an
alternative to compression molding, the core and/or intermediate
layer(s) may be formed by injection molding or other suitable
technique.
[0061] The next step involves forming a cover around the golf ball
core. The core, including the center and any intermediate layers,
may be supported within a pair of cover mold-halves by a plurality
of retractable pins. The retractable pins may be actuated by
conventional means known to those of ordinary skill in the art.
[0062] After the mold halves are closed together with the pins
supporting the core, the cover material is injected into the mold
in a liquid state through a plurality of injection ports or gates,
such as edge gates or sub-gates. With edge gates, the resultant
golf balls are all interconnected and may be removed from the mold
halves together in a large matrix. Sub-gating automatically
separates the mold runner from the golf balls during the ejection
of the golf balls from mold halves.
[0063] The retractable pins may be retracted after a predetermined
amount of cover material has been injected into the mold halves to
substantially surround the core. The liquid cover material is
allowed to flow and substantially fill the cavity between the core
and the mold halves, while maintaining concentricity between the
core and the mold halves. The cover material is then allowed to
solidify around the core, and the golf balls are ejected from the
mold halves and subjected to finishing processes, including
coating, painting, and/or other finishing processes, including
processes in accordance with examples of this invention, as will be
described in more detail below.
B. General Description of Thermoplastic Elastomer/Polyolefin Blend
Containing Hydrophobic TPU
[0064] Hydrophobic TPU is an effective compatibilizer for blends of
thermoplastic elastomers such as thermoplastic polyurethane (TPU)
and polyolefins. A compatibilizer provides the ability to combine
materials and produce a blend with acceptable and/or improved
properties by making the materials compatible or miscible.
[0065] A compatibilized blend comprises thermoplastic elastomer,
polyolefin, and an effective amount of hydrophobic thermoplastic
polyurethane (hydrophobic TPU) as a compatibilizer. The
compatibilized blend may form part of the cover layer, for example,
an inner layer of the cover layer, or may form one of the
intermediate or inner layers between the core and the cover layer.
The compatibilized blend is applied to a golf ball in any suitable
manner such as with a molding process step.
C. Aspects of Invention
[0066] An aspect of this invention relate to golf balls having a
layer formed by a compatibilized blend of thermoplastic elastomer
and polyolefin, and an effective amount of hydrophobic
thermoplastic polyurethane (hydrophobic TPU) as a
compatibilizer.
[0067] In one aspect the compatibilized blend is used as at least
one intermediate layer of a golf ball. In other aspects, the
compatibilized blend is used as at least one outer layer of a golf
ball.
[0068] Given the general description of various example aspects of
the invention provided above, more detailed descriptions of various
specific examples of golf ball structures according to the
invention are provided below.
D. Detailed Description of Example Golf Balls, and Methods
According to Aspects of the Invention
[0069] The following discussion and accompanying figures describe
various example golf balls in accordance with aspects of the
present invention. When the same reference number appears in more
than one drawing, that reference number is used consistently in
this specification and the drawings to refer to the same or similar
parts throughout.
[0070] Aspects of the invention utilize a compatibilized blend of
thermoplastic elastomer and polyolefin and an effective amount of a
hydrophobic thermoplastic polyurethane (hydrophobic TPU) as a
compatibilizer. In particular, the thermoplastic elastomer is
thermoplastic polyurethane (TPU).
[0071] The compatibilized blend, as applied as at least one layer
of a golf ball, provides effective moisture protection to the golf
ball. In particular, the compatibilized blend provides a moisture
barrier layer having a Water Vapor Transmission Rate (WVTR) of less
than 1300, after 168 hrs at 25.degree. C. and 50% relative humidity
for instance of less than 1000, preferably less than 750.
[0072] The Shore D hardness of a layer formed by the compatibilized
blend is between 20 and 65. "Shore D hardness" refers to a measure
of the hardness of a material by a durometer, and especially the
material's resistance to indentation. Shore D hardness may be
measured with a durometer directly on the curved surface of the
core, layer, cover, etc., according to ASTM method D2240. In other
embodiments, the hardness may be measured using standard
plaques.
[0073] If the compatibilized blend is applied as an inner or
intermediate layer, the shore D hardness is generally between 30
and 65. If the compatibilized blend is applied as an inner layer of
the cover layer, the shore D hardness is generally between 30 and
65. An alternative scale to Shore D is Shore A hardness. Shore A
hardness is generally between 60 to 99.
[0074] The specific gravity of the layer is greater than 0.80. The
specific gravity of the composite of layers of a golf ball should
be sufficiently high enough to approach but not exceed the USGA
limit of 1.620 oz. in order to have a USGA conforming ball.
"Specific gravity (SG)" refers to the conventional meaning of the
ratio of the density of a given solid (or liquid) to the density of
water at a specific temperature and pressure.
[0075] Hydrophobic TPU is described in US Publication 20090192262
and is a semi crystalline, thermoplastic polyurethane which is
comprised of the reaction product of (1) a hydrophobic polyol, (2)
a polyisocyanate, and (3) a linear chain extender containing 5
carbon atoms or 7 to 12 carbon atoms; wherein the hydrophobic
polyol has a number average molecular weight which is within the
range of about 1,000 to about 4,000; wherein the semi crystalline,
thermoplastic polyurethane has a weight average molecular weight
which is within the range of 50,000 to 1,000,000; and wherein the
semi crystalline, thermoplastic polyurethane has a melting point
which is within the range of 80.degree. C. to 150.degree. C. US
Publication 20090192262 is hereby incorporated by reference in its
entirety.
[0076] The hydrophobic polyol can be a diol of a conjugated
diolefin monomer, a polyisobutylene diol, a polyester polyol
prepared from fatty diols and/or fatty diacids, or mixtures
thereof. For instance, the hydrophobic polyol can be prepared from
dimer fatty alcohols and/or dimer fatty acids. The diols of
conjugated olefin monomers that can be used include hydrogenated
polybutadienediols, and hydrogenated polyisoprene diol.
Hydrogenated polybutadiene polyols are sold by Mitsubishi Chemical
Corporation under the trade name POLYTAIL, and Kraton polyols sold
by Kraton Polymers of Houston, Tex.
[0077] Dimeric acid polyester polyols may contain from about 18 to
about 44 carbon atoms Dimer acids (and esters thereof) are a well
known commercially available class of dicarboxylic acids (or
esters). The dimer acid material will usually contain 26 to 44
carbon atoms. Particularly, examples include dimer acids (or
esters) derived from C.sub.18 and C.sub.22 unsaturated
monocarboxylic acids (or esters) which will yield, respectively,
C.sub.36 and C.sub.44 dimer acids (or esters). Dimer acids derived
from C.sub.18 unsaturated acids, which include acids such as
linoleic and linolenic are particularly well known (yielding
C.sub.36 dimer acids). The dimer acid products will normally also
contain a proportion of trimer acids (C.sub.54 acids when using
C.sub.18 starting acids), possibly even higher oligomers and also
small amounts of the monomer acids. Several different grades of
dimer acids are available from commercial sources and these differ
from each other primarily in the amount of monobasic and trimer
acid fractions and the degree of unsaturation. Priplast.TM.
polyester polyols are branched C.sub.36 dimerized fatty acids which
are particularly useful as the hydrophobic polyol. Priplast.TM.
polyester polyols are commercially available from Uniqema of Gouda,
Netherlands. The hydrophobic polyol used in synthesizing the
hydrophobic TPU will typically have a number average molecular
weight which is within the range of about 1,500 to about 4,000 and
a number average molecular weight which is within the range of
about 2,000 to about 3,000.
[0078] The linear chain extender used in making the hydrophobic TPU
will typically be of the structural formula:
##STR00001##
wherein n represents the integer 5 or an integer from 7 to 12.
Accordingly, the linear chain extender may be selected from the
group consisting of 1,5-pentane diol, 1,7-heptane diol, 1,8-octane
diol, 1,9-nonane diol, 1,10-decane diol, 1,11-undecane diol,
1,12-dodecane diol, and mixtures thereof.
[0079] The polyisocyanate may be a diisocyanate such as aliphatic
diisocyanates and aromatic diisocyanates. Multifunctional
isocyanate compounds, i.e., triisocyanates, etc., which cause
crosslinking, are generally avoided and thus the amount used, if
any, is generally less than 4 mole percent and preferably less than
2 mole percent based upon the total moles of all of the various
isocyanates used. Suitable diisocyanates include aromatic
diisocyanates such as: 4,4'-methylene bis-(phenyl isocyanate)
(MDI); m-xylene diisocyanate (XDI), phenylene-1-4-diisocyanate,
naphthalene-1,5-diisocyanate,
diphenylmethane-3,3'-dimethoxy-4,4'-diisocyanate, and toluene
diisocyanate (TDI); as well as aliphatic diisocyanates such as
isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI),
decane-1,10-diisocyanate, and
dicyclohexylmethane-4,4'-diisocyanate. Dimers and trimers of the
above diisocyanates may also be used as well as a blend of two or
more diisocyanates may be used.
[0080] The polyisocyanate may be in the form of a low molecular
weight polymer or oligomer which is end capped with an isocyanate.
For example, the hydroxyl terminated polyether intermediate
described above may be reacted with an isocyanate-containing
compound to create a low molecular weight polymer end capped with
isocyanate. In the TPU art, such materials are normally referred to
as pre-polymers. Such pre-polymers normally have a number average
molecular weight (Mn) which is within the range of about 500 to
about 10,000.
[0081] The mole ratio of the one or more diisocyanates is generally
from about 0.95 to about 1.05, or from about 0.98 to about 1.03
moles per mole of the total moles of the one or more hydrophobic
polyols and the one or more chain extenders. The molar ratio of the
chain extender to the polyol will typically be within the range of
about 0.3:1 to 10:1 and will more typically be within the range of
about 0.4:1 to 5:1. The molar ratio of the chain extender to the
polyol may be within the range of about 0:5:1 to 3:1 or the range
of about 0.5:1 to 2:1.
[0082] US Publication 20090192262 further describes various
processes of making the hydrophobic TPU. Any suitable method is
acceptable for the present application.
[0083] Catalysts such as stannous and other metal carboxylates as
well as tertiary amines may be used to prepare the hydrophobic TPU.
Examples of metal carboxylates catalysts include stannous octoate,
dibutyl tin dilaurate, phenyl mercuric propionate, lead octoate,
iron acetylacetonate, magnesium acetylacetonate, and the like.
Examples of tertiary amine catalysts include triethylene diamine,
and the like. The amount of the one or more catalysts is generally
from about 50 to about 100 parts by weight per million parts by
weight of the end TPU polymer formed.
[0084] The weight average molecular weight (Mw) of the hydrophobic
TPU polymer range from about 50,000 to about 500,000 Daltons, from
about 100,000 to about 500,000 Daltons, and from about 120,000 to
about 300,000 Daltons. The Mw of the TPU polymer is measured
according to gel permeation chromatography (GPC) against
polystyrene standard.
[0085] When a higher molecular weight hydrophobic TPU polymer is
desired, it can be achieved by using a small amount of a cross
linking agent having an average functionality greater than 2.0 to
induce cross linking. The amount of cross linking agent used is
less than 2 mole percent of the total moles of chain extender, or
less than 1 mole percent. Less than 1 mole percent of the chain
extender may be replaced with trimethylol propane (TMP). The cross
linking is accomplished by adding a cross linking agent having an
average functionality greater than 2.0 together with the
hydrophobic polyol, the isocyanate compound, and chain extender in
the reaction mixture to manufacture the TPU polymer. The amount of
cross linking agent used in the reaction mixture to make the TPU
polymer will depend on the desired molecular weight and the
effectiveness of the particular cross linking agent used. Usually,
less than 2.0 mole percent, or less than 1.0 mole percent, based on
the total moles of chain extender used in making the TPU polymer
are used. The level of cross linking agent used is generally from
about 0.05 mole percent to about 2.0 mole percent based on the
total moles of chain extender.
[0086] The cross linking agents can be any monomeric or oligomeric
materials which have an average functionality of greater than 2.0
and have the ability to cross link the TPU polymer. Such materials
are well known in the art of thermoset polyurethanes such as
trimethylol propane (TMP) and pentaerythritol.
[0087] The hydrophobic TPU has a melting point which is within the
range of about 80.degree. C. to about 150.degree. C. It will
typically have a melting point which is within the range of about
90.degree. C. to about 145.degree. C., and will more typically have
a melting point which is within the range of about 110.degree. C.
to about 140.degree. C.
[0088] Hydrophobic TPU is effective as a compatibilizer for
thermoplastic elastomer/polyolefin blends, in particular
TPU/polyolefin blends.
[0089] The thermoplastic elastomers may be any suitable elastomer
including but not limited to TPE, TPO, TPU, SEB, SBS, SEBS, PEBA,
TPV, and TPR. In particular, the thermoplastic elastomer is
thermoplastic polyurethane (TPU).
[0090] The TPU suitable for combining with the hydrophobic TPU is a
product of a reaction between polyurethane prepolymer and a curing
agent. The polyurethane prepolymer is a product formed by a
reaction between a polyol and a diisocyanate. Often, a catalyst is
employed to promote the reaction between the curing agent and the
polyurethane prepolymer. Further chain extenders may be used to
increase the molecular weight of the polyurethane.
[0091] "Polyisocyanate" refers to an organic molecule having two or
more isocyanate functional groups (e.g., a diisocyanate).
Polyisocyanates useful herein may be aliphatic or aromatic, or a
combination of aromatic and aliphatic, and may include, but are not
limited to, diphenyl methane diisocyanate (MDI), toluene
diisocyanate (TDI), hexamethylene diisocyanate (HDI),
dicyclohexylmethane diisocyanate (H.sub.12MDI), isoprene
diisocyanate (IPDI), etc.
[0092] "Polyol" refers to an organic molecule having two or more
hydroxyl functional groups.
[0093] Catalysts such as stannous and other metal carboxylates as
well as tertiary amines may be used to prepare the TPU. Examples of
metal carboxylates catalysts include stannous octoate, dibutyl tin
dilaurate, phenyl mercuric propionate, lead octoate, iron
acetylacetonate, magnesium acetylacetonate, and the like. Examples
of tertiary amine catalysts include triethylene diamine, and the
like. The amount of the one or more catalysts is low, generally
from about 50 to about 100 parts by weight per million parts by
weight of the end TPU polymer formed
[0094] "Chain extender" refers to an agent which increases the
molecular weight of a lower molecular weight polyurethane to a
higher molecular polyurethane. Chain extenders may include one or
more diols such as ethylene glycol, diethylene glycol, butane diol,
hexane diol, etc.; triols such as trimethylol propane, glycerol,
etc.; and polytetramethylene ether glycol, etc.
[0095] The TPU generally has a Shore D hardness of between about 20
and about 60 and a specific gravity of greater than about 1.2. The
TPU generally has a weight average molecular weight of from about
20,000 to about 500,000.
[0096] U.S. Pat. No. 6,054,533, hereby incorporated by reference,
describes types of conventional thermoplastic polyurethanes and
techniques for their synthesis. Examples of suitable thermoplastic
polyurethanes include ESTANE.RTM. 58133, ESTANE.RTM. 58134 and
ESTANE.RTM. 58144, which are commercially available from Lubrizol
of Cleveland, Ohio.
[0097] The polyolefin utilized in such compatibilized blend may be
made from olefin, monomers containing from 2 to about 6 carbon
atoms, such as polyethylene (including high density polyethylene,
low density polyethylene, linear low density polyethylene and the
like), polypropylene (including atactic polypropylene, syndiotactic
polypropylene, and blends of polypropylene with elastomers),
polybutylene, and copolymers of such olefin monomers. The weight
average molecular weight of such polyolefins is generally from
about 40,000 to about 2,000,000, and preferably from about 100,000
to about 1,500,000.
[0098] The amount of the thermoplastic elastomers in the blend is
from about 5 percent to about 95 percent by weight based upon the
total weight of the thermoplastic elastomer and polyolefin,
typically about 15 percent to about 85 percent, and also between 20
percent and about 80 percent, or between 30 percent and 70 percent,
and the amount of the polyolefin is a complementary amount,
generally from about 5 percent by weight to about 95 percent by
weight based upon the total weight of the thermoplastic elastomer
and polyolefin.
[0099] The amount of the compatibilizing agent of the present
invention utilized to form the compatibilized blend depends upon
the type of thermoplastic elastomers, the type of particular
polyolefin, and the like. Generally, the amount of compatibilizing
agent is from about 0.25 to about 15 parts by weight, typically
about 0.5 or 0.75 to about 6 or 10 parts by weight for every 100
parts by weight of the thermoplastic elastomer and the polyolefin
blend.
[0100] The thermoplastic elastomer, polyolefin, and hydrophobic TPU
are mixed or blended in a suitable manner. The mixing can utilize
conventional melt processing techniques and can either be batch or
continuous such as through the use of a single or a twin screw
extruder. The mixing temperature is generally above the melting
point of the TPU, and the hydrophobic TPU. Such temperatures are
generally from about 180.degree. C. to about 240.degree. C. The
mixing time will naturally vary depending upon the amount of
components being blended together, the mixing equipment used, and
the mixing temperature.
[0101] Additional additives optionally may be incorporated into the
compatibilized blend, such as flow additives, mar/slip additives,
adhesion promoters, thickeners, gloss reducers, flexibilizers,
cross-linking additives, isocyanates or other agents for toughening
or creating scratch resistance, optical brighteners, UV absorbers,
and the like. The amount of such additives usually ranges from 0 to
about 20 wt %, often from 0 to about 6 wt %.
[0102] After being compatibilized, such thermoplastic polyolefin
blends exhibit improved properties such as impact resistance, good
tensile strength, low delamination, good tear resistance, low
abrasion, and the like over noncompatibilized blends of the same
two polymers as fully shown in the various examples.
[0103] The compatibilized blend is applied to a golf ball with one
molding process step, for example. The method of applying the resin
is not limited.
[0104] The thickness of the applied blend (after drying, curing,
cooling, hardening, or setting) typically ranges from of about 0.5
to about 5.0 mm, and in some examples, from about 0.75 to about 3.0
mm.
[0105] The golf ball body of the present invention has no
limitation on its structure and includes a one-piece golf ball, a
two-piece golf ball, a multi-piece golf ball comprising at least
three layers, and a wound-core golf ball. The present invention can
be applied for all types of the golf ball.
EXAMPLE
[0106] The tables below display 6 different blends and their
corresponding Moisture Vapor
[0107] Transmission Rates (WVTR). FIG. 4 displays the trend in
vapor transmission as the % hydrophobic TPU (H-TPU) is increased
from 0% to 5% to 10%. Blend 6 has the lowest transmission but is
too hard.
Blends:
TABLE-US-00001 [0108] Existing Cover Blend Reduced WVTR Blends
Blend # Estane grade 1 2 3 4 5 6 58219 75% 50% 40% 63% 60% 58280
25% 50% 60% 32% 30% 25% H-TPU 0% 0% 0% 5% 10% 0% ETE 50DT3 75%
Performance:
TABLE-US-00002 [0109] Blend # 1 2 3 4 5 6 Shore A 86 85 84 87 86 92
Hardness, 5 sec ASTM D2240 Moisture vapor 930 1100 1500 1200 1000
650 transmission, Upright Cup 25 C, 50% RH 5 mil film Loss, g/m2
after 168 hrs
III. CONCLUSION
[0110] The present invention is described above and in the
accompanying drawings with reference to a variety of example
structures, features, elements, and combinations of structures,
features, and elements. The purpose served by the disclosure,
however, is to provide examples of the various features and
concepts related to the invention, not to limit the scope of the
invention. One skilled in the relevant art will recognize that
numerous variations and modifications may be made to the
embodiments described above without departing from the scope of the
present invention, as defined by the appended claims. For example,
the various features and concepts described above in conjunction
with the figures may be used individually and/or in any combination
or subcombination without departing from this invention.
* * * * *